WO2021088457A1 - Method for producing diethylenetriaminepenta(methylene-phosphonic acid) - Google Patents

Method for producing diethylenetriaminepenta(methylene-phosphonic acid) Download PDF

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WO2021088457A1
WO2021088457A1 PCT/CN2020/109680 CN2020109680W WO2021088457A1 WO 2021088457 A1 WO2021088457 A1 WO 2021088457A1 CN 2020109680 W CN2020109680 W CN 2020109680W WO 2021088457 A1 WO2021088457 A1 WO 2021088457A1
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acid
formaldehyde
hydrochloric acid
diethylenetriamine
reaction
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程终发
林学洲
齐晓婧
宋盟盟
周响
刘全华
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山东泰和水处理科技股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl

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  • the invention belongs to the technical field of industrial water treatment agent chemical industry, and specifically relates to a production process of diethylenetriamine pentamethylene phosphonic acid.
  • Diethylene triamine pentamethylene phosphonic acid also known as diethylene triamine pentamethylene phosphonic acid, etc.
  • DTPMPA Diethylene triamine pentamethylene phosphonic acid
  • DTPMPA can dissociate into ten positive ions and ten negatively charged ions in water, and can form a polycyclic chelate with Ca 2+ and Mg 2+ in water.
  • This macromolecular chelate is dispersed in a loose manner.
  • the normal crystallization of magnesium and calcium scale is destroyed, and it can form stable complexes with Fe, Cu, Mg and other metal ions in a wide pH range, with low toxicity, easy availability of raw materials, low price and Avoid acidification treatment of the raw water quality, and it can be "alkaline operation" and other characteristics, and gradually become one of the main components of the composite water quality stabilizer.
  • DTPMPA has a good scale inhibition effect on calcium carbonate, magnesium silicate, calcium sulfate, etc. in water.
  • DTPMPA is a non-equivalent chelating agent. It has a "limiting effect" in itself, which can prevent dozens to hundreds of calcium, magnesium and sulfate ions from generating scale precipitation by one molecule. This is its unique scale inhibition performance.
  • DTPMPA is generally used as a scale and corrosion inhibitor for circulating cooling water and boiler water, and is especially suitable for alkaline circulating cooling water as a scale and corrosion inhibitor without adjusting pH, and can be used for oilfield water injection and cooling water with high barium carbonate content. Scale and corrosion inhibitor for boiler water; this product is used alone in the compound medicament without adding a dispersant, and the amount of dirt deposition is still very small.
  • DTPMPA can also be used as a peroxide stabilizer, a chelating agent for textile printing and dyeing, a dispersant for pigments, an oxygen delignification stabilizer, a trace element carrier in fertilizers, and a concrete additive. In addition, it has also been widely used in papermaking, electroplating, metal pickling and cosmetics. It can also be used as a stabilizer for oxidizing fungicides.
  • the industrial synthesis method of DTPMPA mostly uses the synthesis process of formaldehyde, diethylene triamine and phosphorous acid as raw materials. Usually, it is produced by mixing and neutralizing diethylene triamine with phosphorous acid and hydrochloric acid, and then adding formaldehyde to the mixed liquid to react. the way. In order to completely react diethylenetriamine and phosphorous acid in production, a large amount of excess formaldehyde is usually added. The recovery and treatment of excess formaldehyde consumes a lot of resources, and as the concentration of the reaction system decreases, the main reaction rate gradually slows down. The increase in the relative rate of the reaction not only increases the content of the by-product hydroxymethylphosphonic acid, but also leads to a long production cycle. The above deficiencies are not conducive to the industrial production of DTPMPA.
  • the present invention provides a process for the production of diethylenetriamine pentamethylene phosphonic acid.
  • the process increases the concentration of materials in the reaction system, shortens the reaction time, and improves the effective active component by changing the method of material addition.
  • the yield of ethylene triamine pentamethylene phosphonic acid reduces product cost.
  • a production method of diethylenetriamine pentamethylene phosphonic acid mainly includes the following steps:
  • n (diethylene triamine) : n (H3PO3) : n (CH2O) 1: (4.5 ⁇ 5.5): (5.0 ⁇ 7.0);
  • n (diethylene triamine) : n (H3PO3) : n (CH2O) 1: (4.8 ⁇ 5.0): (5.5 ⁇ 6.0).
  • the mass percentage content of the hydrochloric acid in the above step (1) is 15 to 36%; preferably, the mass percentage content of the hydrochloric acid is 30 to 35%.
  • the phosphorous acid in the above step (1) can be any of phosphorous acid crystals and phosphorous acid aqueous solution.
  • the formaldehyde dropping temperature is 95-120°C; wherein, preferably, the formaldehyde dropping temperature is 110-120°C.
  • step (2) the dropwise addition flow rate of the formaldehyde shows an increasing trend with the time of the dropwise addition.
  • the amount of formaldehyde entering the kettle in the first stage accounts for 60-90% by mass of the total amount of formaldehyde in the process; wherein, preferably, the amount of formaldehyde entering the kettle in the first stage is 75-85 of the total amount of formaldehyde. %; more preferably 80%.
  • the additional amount of hydrochloric acid in the above step (3) is 0-20% of the amount of hydrochloric acid added in step (1); wherein, preferably, the amount of additional hydrochloric acid is 5 to 20% of the amount of hydrochloric acid added in step (1). 10%.
  • the beneficial effect of the present invention the process adopts the method of dropping formaldehyde in batches.
  • the concentration of reactants in the system in different time periods is adjusted by gradually increasing the speed of formaldehyde entering the kettle in the early stage, and by external evaporation and concentration and supplementary addition in the later period.
  • the reaction rate is accelerated, which not only effectively inhibits the production of by-product hydroxymethylphosphonic acid, but also improves the conversion rate and product yield of the effective active component diethylenetriamine pentamethylenephosphonic acid, and shortens
  • the total reaction time is reduced, and the production cost is reduced.
  • the process method is simple, safe and easy to operate, and is beneficial to industrialized production.
  • Figure 1 is a schematic diagram of the reaction process of the present invention.

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Abstract

Disclosed in the present invention is a process for producing diethylenetriaminepenta(methylene-phosphonic acid). The process comprises the following specific operation steps: (1) adding measured hydrochloric acid, diethylenetriamine, and phosphorous acid to a reaction kettle in sequence, continuously stirring in the reaction kettle, and maintaining the temperature to be less than or equal to 50°C; (2) heating to a certain temperature, adding a part of an aqueous formaldehyde solution dropwise at different flow rates, completing dropwise addition, preserving heat, and performing concentration; and (3) complementing the hydrochloric acid and heating to 110-120°C, adding the remaining amount of the aqueous formaldehyde solution dropwise, completing dropwise addition, preserving the heat for reaction, performing external evaporation, and performing dilution, cooling, and acidity adjustment to obtain a qualified finished product. In the present invention, the reaction rate is accelerated, the production of a by-product, i.e., hydroxymethylphosphonic acid, is effectively inhibited, and a conversion rate and product yield of an effective active component, i.e., diethylenetriaminepenta(methylene-phosphonic acid), are improved. Moreover, a total reaction time is shortened, and a production cost is reduced. The process method is simple, safe, easy to operate, and beneficial to industrial production.

Description

一种二乙烯三胺五亚甲基膦酸的生产方法A kind of production method of diethylene triamine pentamethylene phosphonic acid 技术领域Technical field
本发明属于工业水处理剂化工技术领域，具体涉及一种二乙烯三胺五亚甲基膦酸的生产工艺。The invention belongs to the technical field of industrial water treatment agent chemical industry, and specifically relates to a production process of diethylenetriamine pentamethylene phosphonic acid.
背景技术Background technique
二乙烯三胺五亚甲基膦酸(DTPMPA)，又称二乙烯三胺五甲叉膦酸等，是一种有机膦酸类阻垢缓蚀剂，其分子结构中含有的C-P键，与无机聚合磷酸盐总的P-O-P或C-O-P键相比具有更强的键能，结合更牢固，因此，具有高温热稳定性，同时缓蚀性能比无机聚合磷酸盐强4～7倍。Diethylene triamine pentamethylene phosphonic acid (DTPMPA), also known as diethylene triamine pentamethylene phosphonic acid, etc., is a kind of organic phosphonic acid scale and corrosion inhibitor. The CP bond contained in its molecular structure and Compared with the total POP or COP bond of inorganic polymer phosphate, it has stronger bond energy and stronger bonding. Therefore, it has high temperature thermal stability and corrosion inhibition performance is 4 to 7 times stronger than that of inorganic polymer phosphate.
同时，DTPMPA在水中能够离解成十个正离子和含十个负电荷的离子，能与水中Ca 2+、Mg 2+等形成多元环螯合物，这个大分子螯合物以松散的方式分散于水中，使镁、钙垢的正常结晶遭到破坏，且能在较宽的pH范围内与Fe、Cu、Mg等金属离子形成稳定的络合物，毒性小、原料易得、价格低廉以及避免对原水水质的酸化处理，可以“碱性运行”等特点，逐渐成为复合水质稳定剂的主要组成之一。因此，DTPMPA对水中的碳酸钙、硅酸镁、硫酸钙等具有较好的阻垢作用。DTPMPA为非当量的螯合剂，本身有“溶限效应”，可以由一个分子阻止几十个到几百个钙、镁离子与硫酸根离子等产生水垢沉淀，这是它特有的阻垢性能。 At the same time, DTPMPA can dissociate into ten positive ions and ten negatively charged ions in water, and can form a polycyclic chelate with Ca 2+ and Mg 2+ in water. This macromolecular chelate is dispersed in a loose manner. In water, the normal crystallization of magnesium and calcium scale is destroyed, and it can form stable complexes with Fe, Cu, Mg and other metal ions in a wide pH range, with low toxicity, easy availability of raw materials, low price and Avoid acidification treatment of the raw water quality, and it can be "alkaline operation" and other characteristics, and gradually become one of the main components of the composite water quality stabilizer. Therefore, DTPMPA has a good scale inhibition effect on calcium carbonate, magnesium silicate, calcium sulfate, etc. in water. DTPMPA is a non-equivalent chelating agent. It has a "limiting effect" in itself, which can prevent dozens to hundreds of calcium, magnesium and sulfate ions from generating scale precipitation by one molecule. This is its unique scale inhibition performance.
DTPMPA一般用作循环冷却水和锅炉水的阻垢缓蚀剂，特别适用于碱性循环冷却水中作为不调pH的阻垢缓蚀剂，并可用于含碳酸钡高的油田注水和冷却水、锅炉水的阻垢缓蚀剂；在复配药剂中单独使用本品，无需投加分散剂，污垢沉积量仍很小。DTPMPA也可用作过氧化物稳定剂、纺织印染用螯合剂、颜料的分散剂、氧脱木素稳定剂、化肥中微量元素携带剂、混凝土添加剂。此外，在造纸、电镀、金属酸洗和化妆品等方面也得到了广泛应用。还可作氧化性杀菌剂的稳定剂。DTPMPA is generally used as a scale and corrosion inhibitor for circulating cooling water and boiler water, and is especially suitable for alkaline circulating cooling water as a scale and corrosion inhibitor without adjusting pH, and can be used for oilfield water injection and cooling water with high barium carbonate content. Scale and corrosion inhibitor for boiler water; this product is used alone in the compound medicament without adding a dispersant, and the amount of dirt deposition is still very small. DTPMPA can also be used as a peroxide stabilizer, a chelating agent for textile printing and dyeing, a dispersant for pigments, an oxygen delignification stabilizer, a trace element carrier in fertilizers, and a concrete additive. In addition, it has also been widely used in papermaking, electroplating, metal pickling and cosmetics. It can also be used as a stabilizer for oxidizing fungicides.
DTPMPA的工业合成方法多采用甲醛、二乙烯三胺和亚磷酸为原料的合成工艺，通常 采用先将二乙烯三胺和亚磷酸及盐酸混合中和，再向混合液中滴加甲醛反应的生产方式。生产中为使二乙烯三胺和亚磷酸完全反应，通常加入大量过量的甲醛，对过量甲醛的回收和处理需消耗大量资源，且随着反应体系浓度的降低，主反应速率逐渐变缓，副反应相对速率增加，不但增加了副产物羟甲基膦酸的含量，而且导致生产周期长。以上不足均不利于DTPMPA的工业化生产。The industrial synthesis method of DTPMPA mostly uses the synthesis process of formaldehyde, diethylene triamine and phosphorous acid as raw materials. Usually, it is produced by mixing and neutralizing diethylene triamine with phosphorous acid and hydrochloric acid, and then adding formaldehyde to the mixed liquid to react. the way. In order to completely react diethylenetriamine and phosphorous acid in production, a large amount of excess formaldehyde is usually added. The recovery and treatment of excess formaldehyde consumes a lot of resources, and as the concentration of the reaction system decreases, the main reaction rate gradually slows down. The increase in the relative rate of the reaction not only increases the content of the by-product hydroxymethylphosphonic acid, but also leads to a long production cycle. The above deficiencies are not conducive to the industrial production of DTPMPA.
发明内容Summary of the invention
针对上述存在的不足，本发明提供一种二乙烯三胺五亚甲基膦酸的生产工艺，该工艺通过改变物料投加方式，提高反应体系物料浓度，缩短反应时间，提高有效活性组分二乙烯三胺五亚甲基膦酸收率，降低产品成本。In view of the above-mentioned shortcomings, the present invention provides a process for the production of diethylenetriamine pentamethylene phosphonic acid. The process increases the concentration of materials in the reaction system, shortens the reaction time, and improves the effective active component by changing the method of material addition. The yield of ethylene triamine pentamethylene phosphonic acid reduces product cost.
本发明目的具体可以通过如下技术方案实现：The purpose of the present invention can be specifically achieved through the following technical solutions:
一种二乙烯三胺五亚甲基膦酸的生产方法，主要包括以下步骤：A production method of diethylenetriamine pentamethylene phosphonic acid mainly includes the following steps:
(1)将计量好的盐酸、二乙烯三胺和亚磷酸依次加入反应釜中，反应釜持续搅拌，保持温度≤50℃，同时开启尾气吸收装置，待中和反应完全后，开始升温；(1) Add the measured hydrochloric acid, diethylenetriamine and phosphorous acid to the reaction kettle in sequence, keep stirring the reaction kettle, keep the temperature ≤50℃, and turn on the exhaust gas absorption device at the same time. After the neutralization reaction is complete, start to heat up;
(2)升温至一定温度，开始控制不同流速滴加部分甲醛水溶液，甲醛滴加结束并110～120℃保温1～2小时，外蒸浓缩至近干；(2) Raise the temperature to a certain temperature, and start to control different flow rates to add part of the formaldehyde aqueous solution. After the formaldehyde dripping is completed, keep it at 110-120°C for 1 to 2 hours, and then steam and concentrate to near dryness;
(3)向体系中补加盐酸并提温至110～120℃，继续滴加余量甲醛水溶液，滴加完毕，继续保温反应0.5～1.0小时后，外蒸至体系无物料采出，经稀释、降温、调酸得合格成品。(3) Add hydrochloric acid to the system and raise the temperature to 110～120℃, continue to add the remaining formaldehyde aqueous solution dropwise, after the dripping is completed, continue the heat preservation reaction for 0.5 to 1.0 hours, and then steam the system until no material is extracted from the system, after dilution , Cooling and adjusting acid to obtain qualified finished products.
上述生产工艺中所述反应物二乙烯三胺、亚磷酸和甲醛的投料摩尔比为n (二乙烯三胺)：n (H3PO3)：n (CH2O)＝1:(4.5～5.5):(5.0～7.0)；作为优选地，n (二乙烯三胺)：n (H3PO3)：n (CH2O)＝1:(4.8～5.0):(5.5～6.0)。 The molar ratio of the reactants diethylene triamine, phosphorous acid and formaldehyde in the above production process is n (diethylene triamine) : n (H3PO3) : n (CH2O) = 1: (4.5～5.5): (5.0 ~7.0); Preferably, n (diethylene triamine) : n (H3PO3) : n (CH2O) = 1: (4.8 ~ 5.0): (5.5 ~ 6.0).
上述步骤(1)中所述盐酸的质量百分比含量为15～36％；作为优选地，盐酸的质量百分比含量为30～35％。The mass percentage content of the hydrochloric acid in the above step (1) is 15 to 36%; preferably, the mass percentage content of the hydrochloric acid is 30 to 35%.
上述步骤(1)中所述盐酸与二乙烯三胺的投料摩尔比为：n (二乙烯三胺)：n (HCl)＝1:(3.0～5.0)； 作为优选地，n (二乙烯三胺)：n (HCl)＝1:(4.0～4.5)。 The molar ratio of hydrochloric acid to diethylene triamine in the above step (1) is: n (diethylene triamine) : n (HCl) = 1: (3.0～5.0); preferably, n (diethylene triamine) Amine) : n (HCl) = 1: (4.0-4.5).
上述步骤(1)中所述亚磷酸可以为亚磷酸晶体、亚磷酸水溶液的任一种。The phosphorous acid in the above step (1) can be any of phosphorous acid crystals and phosphorous acid aqueous solution.
上述步骤(2)中所述甲醛滴加温度为95～120℃；其中，作为优选地，甲醛滴加温度为110～120℃。In the above step (2), the formaldehyde dropping temperature is 95-120°C; wherein, preferably, the formaldehyde dropping temperature is 110-120°C.
上述步骤(2)中所述甲醛滴加流速随滴加时间不同呈递增趋势。In the above step (2), the dropwise addition flow rate of the formaldehyde shows an increasing trend with the time of the dropwise addition.
上述步骤(2)中所述第一阶段入釜甲醛量占工艺甲醛总用量的质量百分比为60～90％；其中，作为优选地，第一阶段入釜甲醛量为甲醛总用量的75～85％；进一步优选为80％。In the above step (2), the amount of formaldehyde entering the kettle in the first stage accounts for 60-90% by mass of the total amount of formaldehyde in the process; wherein, preferably, the amount of formaldehyde entering the kettle in the first stage is 75-85 of the total amount of formaldehyde. %; more preferably 80%.
上述步骤(3)中所述盐酸的补加量为步骤(1)中盐酸投料量的0～20％；其中，作为优选地，补加盐酸量为步骤(1)中盐酸投料量的5～10％。The additional amount of hydrochloric acid in the above step (3) is 0-20% of the amount of hydrochloric acid added in step (1); wherein, preferably, the amount of additional hydrochloric acid is 5 to 20% of the amount of hydrochloric acid added in step (1). 10%.
本发明的有益作用：该工艺采用甲醛分批次滴加的方法，前期通过逐渐增加甲醛入釜速度、后期通过外蒸浓缩和补加的方式来调节不同时间段内体系中反应物的浓度，快速降低体系中亚磷含量，减少反应过程甲醛用量。通过体系提浓，加快了反应速率，不但有效抑制了副产物羟甲基膦酸的产生，提高了有效活性组分二乙烯三胺五亚甲基膦酸的转化率和产品收率，而且缩短了总反应时间，降低了生产成本。该工艺方法简单、安全、易操作，利于工业化生产。The beneficial effect of the present invention: the process adopts the method of dropping formaldehyde in batches. The concentration of reactants in the system in different time periods is adjusted by gradually increasing the speed of formaldehyde entering the kettle in the early stage, and by external evaporation and concentration and supplementary addition in the later period. Quickly reduce the phosphorous content in the system and reduce the amount of formaldehyde in the reaction process. Through the system concentration, the reaction rate is accelerated, which not only effectively inhibits the production of by-product hydroxymethylphosphonic acid, but also improves the conversion rate and product yield of the effective active component diethylenetriamine pentamethylenephosphonic acid, and shortens The total reaction time is reduced, and the production cost is reduced. The process method is simple, safe and easy to operate, and is beneficial to industrialized production.
附图说明Description of the drawings
图1为本发明的反应流程简图。Figure 1 is a schematic diagram of the reaction process of the present invention.
具体实施方式Detailed ways
实施例1Example 1
将2813Kg质量分数71.25％的亚磷酸水溶液和2250Kg质量分数31.50％的盐酸依次加入反应釜中，开启搅拌和尾气回收装置，再向反应釜中缓慢滴加500.0Kg二乙烯三胺，釜内温度控制在50℃以下，中和反应完成后，加热升温使反应釜内温度保持在115±2℃，设置并自动控制甲醛滴加速度分别为：250Kg/h滴加0.5小时，500Kg/h滴加0.5小时，1000Kg/h滴加至第一阶段结束，共计滴加1573Kg质量含量40.73％的甲醛水溶液，115±2℃保温反应1小时后， 先常压后负压条件下外蒸浓缩至近干；停止负压，并向体系中补加225Kg盐酸，控制体系温度为115±2℃，按照200Kg/h流速滴加余量甲醛水溶液共计393Kg，保温0.5小时后，负压外蒸至体系无物料采出，经加水稀释、降温、盐酸调酸度得活性为50.47％的棕黄色透明DTPMPA水溶液5417.6kg，收率(以二乙烯三胺计)为98.30％，副产物羟甲基膦酸的含量为0.74％。Add 2813Kg of 71.25% phosphorous acid aqueous solution and 2250Kg of 31.50% hydrochloric acid to the reactor in turn, turn on the stirring and tail gas recovery device, and then slowly drop 500.0Kg of diethylenetriamine into the reactor, and control the temperature in the reactor. Below 50℃, after the neutralization reaction is completed, heat and increase the temperature to keep the temperature in the reactor at 115±2℃, set and automatically control the formaldehyde dropping acceleration respectively: 250Kg/h for 0.5 hours, 500Kg/h for 0.5 hours , 1000Kg/h was added dropwise to the end of the first stage, a total of 1573Kg of formaldehyde aqueous solution with a mass content of 40.73% was added dropwise. After the reaction was kept at 115±2°C for 1 hour, it was evaporated and concentrated to near dryness under normal pressure and then under negative pressure. Add 225Kg of hydrochloric acid to the system, control the temperature of the system to 115±2℃, and add the remaining formaldehyde solution to a total of 393Kg at a flow rate of 200Kg/h. After holding for 0.5 hours, vacuum externally steam until no material is extracted from the system. After diluting with water, cooling, and adjusting the acidity with hydrochloric acid, 5417.6 kg of a brown-yellow transparent DTPMPA aqueous solution with an activity of 50.47% was obtained, the yield (calculated as diethylenetriamine) was 98.30%, and the content of by-product hydroxymethylphosphonic acid was 0.74%.
实施例2Example 2
将2703Kg质量分数70.69％的亚磷酸水溶液和2441Kg质量分数32.66％的盐酸依次加入反应釜中，开启搅拌和尾气回收装置，再向反应釜中缓慢滴加500.0Kg二乙烯三胺，釜内温度控制在50℃以下，中和反应完成后，加热升温使反应釜内温度保持在115±2℃，设置并自动控制甲醛滴加速度分别为：250Kg/h滴加0.5小时，500Kg/h滴加0.5小时，1000Kg/h滴加至第一阶段结束，共计滴加1716Kg质量含量40.73％的甲醛水溶液，115±2℃保温反应1小时后，先常压后负压条件下外蒸浓缩至近干；停止负压，并向体系中补加225Kg盐酸，控制体系温度为115±2℃，按照200Kg/h流速滴加余量甲醛水溶液共计429Kg，保温0.5小时后，负压外蒸至体系无物料采出，经加水稀释、降温、盐酸调酸度得活性为50.36％的棕黄色透明DTPMPA水溶液5419.50kg，收率(以二乙烯三胺计)为98.12％，副产物羟甲基膦酸的含量为0.63％。Add 2703Kg of 70.69% phosphorous acid aqueous solution and 2441Kg of 32.66% hydrochloric acid to the reaction kettle in turn, turn on the stirring and tail gas recovery device, and then slowly drop 500.0Kg of diethylenetriamine into the reaction kettle, and control the temperature in the kettle. Below 50℃, after the neutralization reaction is completed, heat and increase the temperature to keep the temperature in the reactor at 115±2℃, set and automatically control the formaldehyde dropping acceleration respectively: 250Kg/h for 0.5 hours, 500Kg/h for 0.5 hours , 1000Kg/h was added dropwise to the end of the first stage, a total of 1716Kg of formaldehyde aqueous solution with a mass content of 40.73% was added dropwise. After the reaction was kept at 115±2°C for 1 hour, it was evaporated and concentrated to near dryness under normal pressure and then under negative pressure. Add 225Kg of hydrochloric acid to the system, control the temperature of the system to 115±2℃, and add the remaining formaldehyde solution to a total of 429Kg at a flow rate of 200Kg/h. After holding for 0.5 hours, vacuum externally steam until no material is extracted from the system. After diluting with water, cooling, and adjusting the acidity with hydrochloric acid, 5419.50 kg of a brown-yellow transparent DTPMPA aqueous solution with an activity of 50.36% was obtained, the yield (calculated as diethylenetriamine) was 98.12%, and the content of by-product hydroxymethylphosphonic acid was 0.63%.
对比例1Comparative example 1
将2813Kg质量分数71.25％的亚磷酸水溶液和2250Kg质量分数31.50％的盐酸依次加入反应釜中，开启搅拌和尾气回收装置，再向反应釜中缓慢滴加500.0Kg二乙烯三胺，釜内温度控制在50℃以下，中和反应完成后，加热升温使反应釜内温度保持在115±2℃，按照500Kg/h的流速将2145Kg质量含量40.73％的甲醛水溶液全部滴加入釜，115±2℃保温反应2小时后，先常压后负压条件下外蒸浓缩至体系无物料采出，经加水稀释、降温、盐酸调酸度得活性为50.29％的棕黄色透明DTPMPA水溶液5355.69kg，收率(以二乙烯三胺计)为96.83％，副产 物羟甲基膦酸的含量为5.83％。Add 2813Kg of 71.25% phosphorous acid aqueous solution and 2250Kg of 31.50% hydrochloric acid to the reactor in turn, turn on the stirring and tail gas recovery device, and then slowly drop 500.0Kg of diethylenetriamine into the reactor, and control the temperature in the reactor. Below 50℃, after the neutralization reaction is completed, heat and increase the temperature to keep the temperature in the reactor at 115±2℃. According to the flow rate of 500Kg/h, add 2145Kg of formaldehyde aqueous solution with a mass content of 40.73% to the reactor dropwise, and keep it at 115±2℃. After 2 hours of reaction, the system was evaporated and concentrated under normal pressure and then negative pressure until no material was extracted from the system. After dilution with water, cooling, and acidity adjustment with hydrochloric acid, a brown-yellow transparent DTPMPA aqueous solution with an activity of 50.29% was obtained 5535.69kg. Diethylenetriamine) was 96.83%, and the content of by-product hydroxymethylphosphonic acid was 5.83%.
对比例2Comparative example 2
在甲醛滴加第一阶段结束外蒸后，不补加盐酸，其他条件和实施例1均相同，得活性为50.30％的棕黄色透明DTPMPA水溶液5395.55kg，收率(以二乙烯三胺计)为97.57％，副产物羟甲基膦酸的含量为1.76％。After the first stage of formaldehyde dripping and external steaming, no additional hydrochloric acid was added. The other conditions were the same as those in Example 1. A 50.30% brown-yellow transparent DTPMPA aqueous solution with an activity of 5395.55 kg was obtained. The yield (calculated as diethylene triamine) It was 97.57%, and the content of by-product hydroxymethylphosphonic acid was 1.76%.

Claims (9)

  1. 一种二乙烯三胺五亚甲基膦酸的生产方法，其特征在于，包括以下步骤：A production method of diethylenetriamine pentamethylene phosphonic acid, which is characterized in that it comprises the following steps:
    (1)将盐酸、二乙烯三胺和亚磷酸依次加入反应釜中，反应釜持续搅拌，保持温度≤50℃，同时开启尾气吸收装置，待中和反应完全后，开始升温；(1) Add hydrochloric acid, diethylenetriamine and phosphorous acid to the reaction kettle in sequence, keep stirring the reaction kettle, keep the temperature ≤50°C, and turn on the exhaust gas absorption device at the same time. After the neutralization reaction is complete, start to heat up;
    (2)升温后，不同流速下滴加部分甲醛水溶液，滴加结束并110～120℃保温1～2小时，外蒸浓缩至近干；(2) After the temperature is raised, part of the aqueous formaldehyde solution is added dropwise at different flow rates. After the dropwise addition is completed, the temperature is maintained at 110-120°C for 1 to 2 hours, and it is evaporated and concentrated to near dryness;
    (3)向体系中补加盐酸，继续滴加余量甲醛水溶液，滴加完毕，继续保温反应0.5～1.0小时后，外蒸至体系无物料采出，经稀释、降温、调酸得合格成品。(3) Add hydrochloric acid to the system and continue to add the remaining formaldehyde aqueous solution. After the dripping is completed, the heat preservation reaction is continued for 0.5 to 1.0 hours, and then the system is steamed until no material is extracted from the system. After dilution, cooling, and acid adjustment, a qualified finished product is obtained. .
  2. 根据权利要求1所述的方法，其特征在于，所述的二乙烯三胺、亚磷酸和甲醛的投料摩尔比为The method according to claim 1, wherein the molar ratio of said diethylenetriamine, phosphorous acid and formaldehyde is
    n (二乙烯三胺)：n (H3PO3)：n (CH2O)＝1:4.5～5.5:5.0～7.03。 n (diethylenetriamine) : n (H3PO3) : n (CH2O) =1:4.5～5.5:5.0～7.03.
  3. 根据权利要求1所述的方法，其特征在于，所述的步骤(1)中盐酸的质量百分比含量为15～36％。The method according to claim 1, wherein the mass percentage content of hydrochloric acid in the step (1) is 15 to 36%.
  4. 根据权利要求1所述的方法，其特征在于，所述的步骤(1)中盐酸与二乙烯三胺的投料摩尔比为：n (二乙烯三胺)：n (HCl)＝1:3.0～5.0。 The method according to claim 1, wherein the molar ratio of hydrochloric acid to diethylenetriamine in the step (1) is: n (diethylenetriamine) : n (HCl) = 1:3.0~ 5.0.
  5. 根据权利要求1所述的方法，其特征在于，所述的亚磷酸可以为亚磷酸晶体、亚磷酸水溶液的任一种。The method according to claim 1, wherein the phosphorous acid can be any of phosphorous acid crystals and phosphorous acid aqueous solution.
  6. 根据权利要求1所述的方法，其特征在于，所述的步骤(2)中甲醛滴加温度为95～120℃。The method according to claim 1, characterized in that the formaldehyde dropping temperature in the step (2) is 95-120°C.
  7. 根据权利要求1所述的方法，其特征在于，所述的步骤(2)中甲醛滴加流速随滴加时间逐渐增大。The method according to claim 1, characterized in that, in the step (2), the flow rate of the formaldehyde dropping gradually increases with the dropping time.
  8. 根据权利要求1所述的方法，其特征在于，所述的步骤(2)中入釜甲醛量占工艺甲醛总用量的质量百分比为60～90％。The method according to claim 1, characterized in that the mass percentage of the amount of formaldehyde entering the kettle in the step (2) accounts for the total amount of formaldehyde in the process is 60-90%.
  9. 根据权利要求1所述的方法，其特行在于，所述的步骤(3)中盐酸的补加量为步骤(1)中盐酸投料量的0～20％。The method according to claim 1, wherein the additional amount of hydrochloric acid in step (3) is 0-20% of the amount of hydrochloric acid added in step (1).
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